CN100338132C - Full biological degradable composition and its preparing method and use - Google Patents
Full biological degradable composition and its preparing method and use Download PDFInfo
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- CN100338132C CN100338132C CNB200510020418XA CN200510020418A CN100338132C CN 100338132 C CN100338132 C CN 100338132C CN B200510020418X A CNB200510020418X A CN B200510020418XA CN 200510020418 A CN200510020418 A CN 200510020418A CN 100338132 C CN100338132 C CN 100338132C
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Abstract
The present invention relates to a full biodegradable composition, a preparing method thereof and purposes thereof. The composition comprises the basic components: modified starch having the grain diameter less than or equal to 6.5 micrometers, biodegradable polymers, a nanometer reinforcing agent, a plasticizing agent, a lubricating agent, a reactive type compatibilizer, a crosslinking agent and a biodegradable accelerating agent. The preparation comprises: firstly, the natural starch is dried and treated by superfine modification and plasticizing; then, the treated starch and adjuvant materials are mixed, extruded and granulated in sequence by a reciprocating type single screw extruder and an electromagnetic dynamic mixing extruder. The full biodegradable composition has the advantages of complete biodegradable performance, favorable adaptability, convenient use, wide application range and low cost. Besides, the full biodegradable composition can be used as directly used type resin as well as an adding type parent material used by being mixed with common resin. Products which are manufactured by a conventional method of plastic production and processing and have full or partial biodegradable performance have excellent mechanical performance and favorable water resistance.
Description
Technical field
The present invention relates to be a kind ofly have complete biolytic composition, and the preparation method of said composition and purposes.Specifically be a kind of be that the fundamental sum main raw material has complete biolytic composition and method of making the same and purposes with starch and biodegradable polymkeric substance.
Background technology
Use at present plastic material and goods is increasingly extensive; and the environmental protection problem that brings of conventional plastic industry and based on the shortage of resources problem of petroleum industry; for the consideration of environment protection and searching alternate resources and resource reusable edible, study and use inexorable trend and emphasis that biodegradable material has become the plastics industry exploitation.
Two stages have been experienced in the development of degradable plastic substantially: the fs is photodegradable plastics and biology/light degradation plastic stage, and as reporting to some extent in the documents such as Chinese patent ZL93111901.4, because its goods starch content is low, biological degradability is poor; Subordinate phase is high-content starch and polymer reaction commixed type degradative plastics, as existing report in the documents such as Chinese patent ZL03117398.5.Because its degrade residual thing still has certain harm to environment and animal and plant growth, can not thoroughly solve " solid waste " pollution problem to environment, do not meet the development trend and the world market needs of biological decomposition plastic, just progressively entered the novel full biological decomposition plastics of phase III at present and substitute.
Novel full biological decomposition plastics are meant that discarded back can short-term absolutely be decomposed into CO by microorganism and bacterium etc. in the composting environment
2Plastic material and goods thereof with innoxious substances such as water can comprise three classes at present.One class is from the biological polyester of body synthetic, as the random copolymer of poly 3-hydroxy butyrate (PHB) with poly-3-hydroxyl valerate (PHV) by microorganism.This class full-biodegradable material is owing to technical sophistication, and difficulty is big, and the difficulty that its annual production improves is big.Another kind of is the full biological decomposition plastics of chemosynthesis, general similar natural polymer, can be that raw material is produced with biochemical products or petrochemicals, much more report and use are arranged at present, as polycaprolactam (PCL) as aliphatic polyester typical case representative, and the poly(lactic acid) of making by fermentation method (PLA), be the materials such as polyester copolymer, polyvinyl alcohol of main component with succsinic acid (Succinic Acid), its goods can include fiber, coating, film (packing) etc., but present goods price is still higher.A class is to be the full biological decomposition plastics of raw material with the natural macromolecular material again, wherein is typical case representative with starch, esterification starch, cellulose acetate, starch and chitosan, Mierocrystalline cellulose is arranged or with the multipolymer of chemosynthesis biodegradable plastic etc.
To be documents such as CN1487008A and CN1354196A had report to the preparation of full biological decomposition plastics to the Chinese patent publication number.CN1487008A provides the preparation method of the full biological decomposition type of a kind of high-performance starch material, be to be raw material with starch, mix between the composite plasticizing by softening agent, gelation promotion, clay seam, prepare full biological decomposition type starch material by simple melt-mixing method.CN1354196A has reported the preparation method of the full biological decomposition material of a kind of starch base, plant amylum and response type auxiliary agent be added in the high-speed mixer mix, when temperature is elevated to 80 ℃-200 ℃, add and can decompose the synthetic macromolecular compound, after discharging is pulverized again through the screw extrusion press extrusion moulding.
The biological decomposition material fully that comprises the existing bibliographical information of above-mentioned two parts of patents, its cost is much lower relatively, but physical and mechanical properties still has much room for improvement, also there is a big difference as comparing with similar common plastics goods on physical and mechanical propertiess such as tensile strength, elongation at break, water resisting property, even have a strong impact on its use.Present full biological decomposition resin type plastics and the contrast of the physical and mechanical properties of common plastics goods (is example with the film) are as shown in table 1:
The contrast of table 1 physical and mechanical properties
| Performance | New LDPE (film grade) (LDPE) | Present full biological decomposition plastics |
| Tensile strength | ≥15MPa | About 10MPa |
| Elongation | ≥500％ | About 250% |
| Water resisting property | Do not absorb water | ≥5％ |
| Biodegradable | Biological decomposition takes place hardly | Complete biological decomposition |
In addition, because what it adopted is that the polyester of one-component or starch content wherein are low, and facility investment is big, the production cost height, the long flow path of material in traditional screw extrusion press, energy consumption is big, and the adaptability of processing materials is restricted, all make the goods raw materials cost be much higher than similar common plastics goods, and the performance of full biological decomposition plastics is limited to, can not be satisfactory.These have all seriously restricted the large-scale production of full biological decomposition plastics and have applied.
Summary of the invention
Deficiency at above-mentioned technology, the present invention at first will provide a kind of novel full biological degradable composition, make it can have good biological decomposition performance and mechanics and water repelling property, has complete biological decomposition performance, adaptability is good, easy to use, applied widely and cost is low, both can be used as direct use type resin, also can be used as the addition type masterbatch that is used for mixing use with ordinary resin, have the goods of biological decomposition performance wholly or in part according to the manufacturing of conventional plastics-production processing mode, adapt to the multiple needs of social production and life.On this basis, further aim of the present invention also comprises the preparation method that this full biological degradable composition is provided, and the purposes of this full biological degradable composition.
Full biological degradable composition provided by the invention is to form through melt blending with auxiliary agents such as starch and nanometer strongthener and biodegradable polymkeric substance.Said composition basic composition is in weight part:
Modification plasticized starch 20-80 part of particle diameter≤6.5 micron,
Biodegradable polymkeric substance 10-60 part that plastics-production allows,
Nanometer strengthener 1-6 part,
Softening agent 2-10 part,
Lubricant 1-6 part,
Reactive compatibilizer 0.5-5 part,
Linking agent 0.1-3 part,
Biological decomposition promotor 0.5-3 part.
Said starch can adopt at least a as in the multiple natural starch such as W-Gum, tapioca (flour), pea starch, wheat starch, potato starch, konjak starch, canna starch in the above-mentioned composition, and through miniaturization and modification processing, this is the important and main component in the full biological degradable composition.
The modification of starch, can use is properties-correcting agent and the starch mixing of using always in the present plastics-production of starch weight 0.5%-5%, or adopts as other usual manners such as pre-plasticising, pre-gelatinizations and carry out the modification processing.Said properties-correcting agent commonly used can comprise as lipid acid such as stearic acid, oxystearic acids or as soaps such as sodium stearate, calcium stearate, Zinic stearas and at least a as in the ionogenic surfactant of various ways such as higher amines salt.Wherein said senior amine salt can comprise that the molecular structure kind contains multiple primary amine, secondary amine, tertiary amine or the quaternary amine of 1-2 long chain hydrocarbon groups, and wherein the carbon atom in each long chain hydrocarbon groups can be 12-22, the dimethyl dialkyl amine salt that uses as existing report etc.In these properties-correcting agent, what preferably recommend is the tensio-active agent of fatty acid.Existing at present report of warp or the equipment that uses and/or mode are carried out the miniaturization processing then.Test shows, making maximum particle diameter≤6.5 of the starch granules after miniaturization is handled micron is essential.Starch is carried out miniaturization and modification handle the activity that can significantly improve starch, therefore under the prerequisite of not remarkably influenced cost, reduce miniaturization to handle the particle diameter of back starch granules be favourable as far as possible.
Said nanometer strengthener can select for use its unidimensional scale of existing report and use in 100nm, especially the following nanometer grade calcium carbonate (CaCO of 50nm
3), clay, polynite, mica, vanadium oxide (V
2O
5), molybdenum oxide (MoO
3) at least a in waiting, wherein with lime carbonate (CaCO
3), clay, polynite be preferred.
After adding the nanoparticle composition, owing between nanoparticle and high molecular both interfaces, have physical action and chemical action simultaneously, thereby can make the interface in conjunction with good, and the specific surface area of nanoparticle is big, the phase interface area of itself and polymkeric substance is also very big, thereby can bear certain load, absorb a large amount of striking energys.When matrix was subjected to impacting, because the existence of homodisperse rigidity nanoparticle produces stress concentration effect, easy excitated matrix on every side produced tiny crack (crazing), and the matrix between the particle also produces surrender simultaneously.Produce viscous deformation, absorb striking energy, promoted the brittle-ductile transition of matrix.And the existence of rigid particles also makes the matrix resin crack propagation be obstructed and passivation, finally stops crackle to be unlikely and develops into destructive cracking.Along with particle diameter diminishes, the specific surface area of particle increases, and the contact area between particle and the matrix increases, and when material is subjected to impacting, can produce more tiny crack and viscous deformation, thereby absorb more striking energy, has significantly improved toughening effect.Test-results shows, the adding of these nano components is very useful to the enhancing that increases substantially composition and mechanical property such as toughness reinforcing.
Biodegradable polymkeric substance in the composition is a kind of synthesis type or natural biodegradable high molecular polymer, as the existing polycaprolactone of reporting and using, poly(lactic acid), polyvinyl alcohol, poly-hydroxyalkyl polyester, poly butyric ester, poly-hydroxyl valerate, polyglycolic acid, polyesteramide, urethane etc., or their segmented copolymer, and in the composition such as vegetable fibre one or more.Wherein preferably recommending composition is that weight ratio is 4/6 the single component and the mixture of segmented copolymer.Biological decomposition promotor composition can be when guaranteeing the composition material mechanical property, and the biological decomposition source of composition material can be provided.
Said biological decomposition promotor is to be the composition of 10-40/60-90 composition form by unsaturated acid or unsaturated acid ester and starch by the weight of unsaturated acid or ester/starch.These unsaturated acid or unsaturated acid ester generally can be selected one or more in common linolic acid, linolenic acid, dodecyl acrylate, vinylformic acid octadecanol ester, the phosphorous acid ester for use.Starch wherein can be the starch of common format, but preferred recommend to adopt be still with said components in the treated starch of same form.
For improving the comprehensive physicals and the processing characteristics of present composition material, for example for making the starch component plasticising in the composition, reduce its degree of crystallinity, improve starch thermoplasticity working ability, increase the consistency between starch and biodegradable macromolecular material, eliminate its boundary defect, improve the mechanical property and the mechanical strength of material, improve water repelling property, and improve the fluid property of composition, reduce machining load, improve the processing characteristics of composition and the surface smoothness of goods, can also select and use corresponding softening agent according to the usual manner of plastics-production, composition such as lubricant and expanding material.For example, can select in the polyalcohols compositions such as ethylene glycol commonly used, butyleneglycol, glycerine, sorbyl alcohol, Xylitol one or more for use, or the softening agent of any one form such as methane amide, urea, stearin, preferably glycerine, sorbyl alcohol and/or Xylitol of special recommendation wherein, can play plastification to starch, reduce the starch crystals degree, improve starch thermoplasticity working ability.Said reactive compatibilizer can be selected in currently reported and/or the various ways reactive compatibilizer that uses, is the acid anhydrides of 0.2%-10% and the grafts of degradable high polymer as at least a carboxylic acid, acid anhydrides or the percentage of grafting that for example can select in comprising carboxylic acid such as undecylenic acid commonly used, maleic anhydride, dodecyl cis-butenedioic anhydride, cis-butenedioic anhydride g-polycaprolactone, cis-butenedioic anhydride grafted polyethylene alcohol and/or anhydrides compound of preferred recommendation; Can also be at the polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene (PP), the polystyrene (PS) that comprise as glycidyl methacrylate (GMA), hydroxyl modification, or from the ethylene-methyl methacrylate zinc multipolymer of aggressiveness (ionic polymer), contain one or more that select in epoxide group or the oxy-compound from aggressiveness SurIyn8920, SurIyn 8660 etc.By the reaction between expanding material and starch and the biodegradable resin, and polymerization between the expanding material self and crosslinked interpenetrating polymer networks (IPN) structure that obtains, can make whole co-mixing system reach good molecular mixing state, realize the molecular mixing level, perhaps microcosmic heterogenetic compatibility, thereby significantly increased the consistency between starch and biodegradable macromolecular material, eliminated boundary defect, improved the mechanical property of material.Linking agent can be selected for use as in the silicane linking agent commonly used in methyl tributanoximo silane, cyclohexyl dimethoxy silane, methyl triacetoxysilane, methyltrimethoxy silane, vinyltrimethoxy silane, epoxy silane, the chloropropyl dimethyl dichlorosilane (DMCS) etc. any, wherein preferred recommendation is cyclohexyl dimethoxy silane, vinyltrimethoxy silane, epoxy silane etc., can make biological decomposing composition in the composition, especially starch to be taken place crosslinked, be used to improve the mechanical strength of material, improve the water resisting property of material simultaneously.Select for use as in fatty acid amide, fatty acid ester, the soap series lubricant agents such as stearic amide, methylene bis stearylamide, ethylene bis stearamide, oxystearic acid, n-butyl stearate, calcium stearate, Magnesium Stearate one or more, compositions such as wherein preferred stearic amide, methylene bis stearylamide, ethylene bis stearamide, can improve composition fluid performance, reduce machining load and improve the surface smoothness of goods.
Be appreciated that thus, for dwindling starch in the composition and the poor properties distance between the biodegradable polymer, when making the starch granular, improved its activity by properties-correcting agent again, and when mixing, added expanding material with biodegradable polymer, improve the consistency of the two, eliminated boundary defect.Simultaneously, linking agent also makes composition that the crosslinked of appropriateness takes place, and strengthens intermolecular reactive force.Therefore mix and reaction by the distribution that realizes molecular level between different components, thereby obtain a kind of polymer molectron of stable, homogeneous, and can have and reach and the close mechanical performance indexs of other thermoplastic resin such as PE, PP.The measure of these polynary increase-volumes and means are actively with tangible to the effect of improving the consistency between each material component in the composition.
The Biodegradable of the full biological degradable composition that the present invention is above-mentioned is 100%, and degradation production is CO
2And H
2O, the degraded index can reach the regulation of ISO14855 (international standard), ASTM D6400-99 (USS) and EN13432:2000 standards such as (European standards), and environment and animal and plant growth are not had any harm.
On the basis of above-mentioned composition essentially consist, can also be according to different use needs, according to the suitable complementary added ingredients of usual manner use of present plastics-production, as constituents such as tinting material, flavouring agent, uvioresistant and/or antioxidant commonly used.The use of these complementary compositions can not influence the basic physicals of above-mentioned composition of the present invention.
Because full biological degradable composition provided by the invention can have excellent mechanical property, biological degradability and good processibility, when can be used as direct use type resin, its adaptability is good, the good mechanical performance of goods, water resisting property is good, has complete Biodegradable, and cost is low, remove the resin that can be used as direct use type, mode according to conventional plastic working, directly on conventional plastics machinery by extruding, injection moulding, means such as blowing are processed into multiple plastics commonly used, as sheet material, film, packing bag, cup, outside the disposable products such as dish, also can be used as cheap addition type masterbatch, interpolation masterbatch type of service according to conventional plastics-production, general-purpose plastics mechanically easily with ordinary resin such as polyethylene (PE), polypropylene (PP) etc. is made the various non-sheet materials that decompose fully, moulding, film, plastics such as packing bag, or with polycaprolactone (PCL), polyvinyl alcohol (PVA), poly(lactic acid) biodegradable polymers such as (PLA) is made biological decomposition plastics fully.As the addition type masterbatch, consumption when it uses and mode are all processed with conventional plastics-production and are as good as, and can be 30%～70% scope equally as its common usage quantity.
Test-results also shows simultaneously, and above-mentioned composition of the present invention is being gratifying aspect the Technological adaptability of the suitability that comprises its processibility and goods etc.When with the composition being the further processing of raw material, processing units there is not any particular requirement, can be on general plastics machinery by extrude, mode such as blowing, injection moulding, pulling-on piece is processed into various plastics, as film, cutlery box, shopping bag, refuse bag, cup, dish, disposable office appliance stationery etc.; By the goods of extruding, modes such as blowing, injection moulding, pulling-on piece obtain, can substitute similar ordinary resin goods fully and in social production and life, use, have extensive applicability.
Above-mentioned full biological degradable composition of the present invention can prepare by following process:
1) ative starch drying treatment:
At least a in the general industry starch, being dried to moisture content as natural ative starchs such as W-Gum, tapioca (flour), pea starch, wheat starch, potato starch, konjak starch, canna starches is 1%-10%.Drying process can be carried out under normal temperature and/or normal pressure, also can 20 ℃-160 ℃ temperature and/or-0.01～-carry out under the reduced pressure of 0.08MPa.
2) preparation of treated starch:
Dried starch is added above-mentioned properties-correcting agent (as the fatty acid tensio-active agent etc.) in the ratio of its weight 0.5-5%, mix and carry out modification and handle, it is standby then it to be refined to maximum particle diameter≤6.5 micron (promptly more than 2000 orders).
3) the preliminary mixing of full biological degradable composition:
With the treated starch in the above-mentioned steps 1, by said proportional with add said softening agent, biodegradable polymer materials and lubricant routine operation mode successively, thorough mixing 3-20min in rotating speed is the high-speed mixer of 1000-5000r/min by plastics-production.Mixing can be carried out at normal temperatures, and 0 ℃-100 ℃ heating or do not carry out all can under the heating condition.
4) melting mixing of full biological degradable composition and finally obtaining:
Mixture melt extrudes granulation in the reciprocating type single screw extrusion machine of routine, and adds the linking agent and the reactive compatibilizer (for example can pass through the side loading hole) of said proportional in extrusion by the routine operation mode of plastics-production.Wherein the preferred operations condition of this reciprocating type single screw extrusion machine can for: extrusion temperature is 100 ℃-180 ℃, and engine speed is 100-400r/min, and the feeding machine rotating speed is 3.0-10.0r/min, and melt pressure is 2.0-3.5MPa.
Particle after the melt pelletization is sent into electromagnetic dynamic plasticizing extruder carry out last mixing granulator, and in extrusion, add the nanometer strengthener and the biological decomposition promotor (can pass through the side loading hole) of said proportional in proportion.Test-results shows, guaranteeing under the prerequisite that complex art effect and economic target allow, the preferred control condition of electromagnetic dynamic plasticizing extruder mixing granulator process carry out can for: service temperature is 120 ℃-250 ℃, engine speed is 100-400r/min, the feeding machine rotating speed is 3.0-20.0r/min, melt pressure is 2.0-3.5MPa, and vibrational frequency is 5-50Hz, and negative pressure of vacuum is 0.02-0.08MPa.Improve temperature and can improve plasticizing capacity equally, but may increase corresponding material side reaction too; Improve engine speed,, shear highly, help the rearrangement of material molecule, also may have a negative impact the plasticizing of material though also can improve production rate.The too for a short time discharge that is unfavorable for gas of vacuum tightness, the excessive part material that then might make is walked and is lost by pump drainage.Test-results shows, used electromagnetic dynamic plasticizing extruder especially with the length-to-diameter ratio during for 36-48 for well, increase its length-to-diameter ratio and can help plastifying, but to corresponding the increasing that require of equipment;
Simultaneous test shows, adopt the full biological degradable composition material of the present invention of aforesaid way preparation, particularly adopt the Electromagnetic Dynamic extruding technology, the heat energy that utilization is converted to by electromagnetic power, pressure can and kinetic energy and finish the conveying of material and plastify extrusion moulding, realized the direct electromagnetism transducing of forcing machine, the dynamic fusion plasticizing of material is mixing, melt Conveying and extruding, and physical construction is integrated, not only the adaptability to material is good, the plasticizing extrusion temperature is low, it is high to extrude stability, can improve the quality of extruding of goods greatly, and energy consumption reduces by 50%, volume weight reduces 70%, manufacturing cost reduces by 50%, noise is little, can have more excellent over-all properties and lower cost than the material of extruding with the common double screw rod, helps applying.
Below example by embodiment again foregoing of the present invention is described in further detail.But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following example.Do not breaking away under the above-mentioned technological thought situation of the present invention, various replacements or change according to ordinary skill knowledge and customary means are made include within the scope of the invention.
Embodiment
Embodiment 1
The weight of each component raw material is formed:
80.0 parts of modified corn starchs
20.0 parts of polycaprolactones
5.5 parts in lime carbonate (50 nanometer)
6.0 parts of glycerine
4.0 parts of stearic amides
2.5 parts of dodecyl cis-butenedioic anhydrides
1.0 parts of vinyltrimethoxy silanes
(10/60) 1.8 part of linolic acid/modified starch composition
Operation steps:
It is 1.5% that W-Gum is dried to moisture content at normal temperatures and pressures.The properties-correcting agent calcium stearate that adds 1.0% (weight) in dried W-Gum is refined to 2200 orders after mixing.Then by said ratio get modified corn starch, glycerine mixes in high-speed mixer, rotating speed 1000r/min, 15 minutes time, add biodegradable polymer poly caprolactone and stearic amide successively by said ratio again, mix.Rotating speed 1200r/min, 12 minutes time, 50 ℃ of temperature.The high material that mixes melt extrudes granulation in reciprocating type single screw extrusion machine, add linking agent vinyltrimethoxy silane and reactive compatibilizer dodecyl cis-butenedioic anhydride by said ratio by the side loading hole in extrusion.Extrude pellet and carry out last mixing granulator by electromagnetic dynamic plasticizing extruder at last, in extrusion, add nano-calcium carbonate and biological decomposition promotor linolic acid/modified starch composition by the side loading hole by said ratio.The working parameter of reciprocating type single screw extrusion machine and electromagnetic dynamic plasticizing extruder is as shown in table 2.
The working parameter of reciprocating type single screw extrusion machine of table 2 and electromagnetic dynamic plasticizing extruder
| The temperature setting (℃) | |||||||||
| Section | One | Two | Three | Four | Five | Six | Seven | Eight | Nine |
| Reciprocating type single screw rod | 120 | 140 | 150 | 130 | 120 | ||||
| Electromagnetic dynamic plasticizing extruder | 130 | 145 | 160 | 170 | 180 | 165 | 140 | 130 | 120 |
The engine speed of single screw extrusion machine: 150r/min, feeding machine: about 5.0r/min, material melts body pressure: about 3.0MPa:
Electromagnetic dynamic plasticizing extruder engine speed: 220r/min, feeding machine: about 6.0r/min, material melts body pressure: about 3.0MPa,
Vibrational frequency: 10Hz, vacuum one: natural exhaust, vacuum two :-0.06MPa.
To make full biological degradable composition as the addition type masterbatch by above-mentioned steps, addition with 60% and polyethylene (PE) blend is processed into various plastics, as disposable products such as sheet material, film, packing bag, cup, dishes.With the film is example, its tensile strength 10-16MPa, elongation at break 250-450%.
Embodiment 2
Each composition weight is formed:
75.0 parts of modified tapioca starch
60 parts of poly(lactic acid)
3.6 parts of clays (60 nanometer)
8.0 parts of butyleneglycols
2.4 parts of methylene bis stearylamides
0.8 part of cis-butenedioic anhydride g-polycaprolactone
1.5 parts in cyclohexyl dimethoxy silane
(25/80) 2.0 part of linolenic acid/tapioca (flour) composition
Tapioca (flour) is reduced pressure under 50 ℃, and (0.06MPa) being dried to moisture content is 5%.The properties-correcting agent stearic acid that adds 2.5% (weight) in dried tapioca (flour) is refined to 2500 orders after mixing.Then by said ratio get modified tapioca starch, butyleneglycol mixes in high-speed mixer, rotating speed 1500r/min, 10 minutes time, add biodegradable polymer poly lactic acid and methylene bis stearylamide successively by said ratio again, mix.Rotating speed 1500r/min, 15 minutes time, 70 ℃ of temperature.The high material that mixes melt extrudes granulation in reciprocating type single screw extrusion machine, add linking agent cyclohexyl dimethoxy silane and reactive compatibilizer cis-butenedioic anhydride g-polycaprolactone by said ratio by the side loading hole in extrusion.Extrude pellet and carry out last mixing granulator by electromagnetic dynamic plasticizing extruder at last, in extrusion, add nanoclay and biological decomposition promotor linolenic acid/tapioca (flour) composition by the side loading hole by said ratio.The working parameter of reciprocating type single screw extrusion machine and electromagnetic dynamic plasticizing extruder is as shown in table 3.
The working parameter of reciprocating type single screw extrusion machine of table 3 and electromagnetic dynamic plasticizing extruder
| The temperature setting (℃) | |||||||||
| Section | One | Two | Three | Four | Five | Six | Seven | Eight | Nine |
| Reciprocating type single screw rod | 110 | 120 | 130 | 120 | 105 | ||||
| Electromagnetic dynamic plasticizing extruder | 120 | 135 | 150 | 160 | 170 | 155 | 145 | 135 | 120 |
The engine speed of single screw extrusion machine: 200r/min, feeding machine: about 4.5r/min, material melts body pressure: about 2.5MPa
Electromagnetic dynamic plasticizing extruder engine speed: 300r/min, feeding machine: about 5.0r/min, material melts body pressure: about 2.2MPa
Vibrational frequency: 5Hz, vacuum one: natural exhaust, vacuum two :-0.08MPa.
To make full biological degradable composition as the addition type masterbatch by above-mentioned steps, addition with 65% and polycaprolactone (PCL) blend, making by injection moulding can complete biolytic sheet material.Its tensile strength 10-20MPa, modulus in tension 〉=500-800MPa
Embodiment 3
Each composition weight is formed:
20 parts of modification pea starches
50 parts of polyvinyl alcohol
3.0 parts of polynites (30 nanometer)
5.5 parts of sorbyl alcohols
6.0 parts of ethylene bis stearamides
0.5 part of the polyethylene terephthalate of hydroxyl modification (PET)
3.0 parts of epoxy silanes
(40/90) 2.5 part of phosphorous acid ester/modified starch composition
With pea starch 150 ℃ and the decompression (0.002MPa) being dried to moisture content under the condition is 10%.The properties-correcting agent sodium stearate that adds 4.0% (weight) in dried pea starch is refined to 3000 orders after mixing.Then by said ratio get the modification pea starch, sorbyl alcohol mixes in high-speed mixer, rotating speed 3000r/min, 5 minutes time, add biodegradable polymer poly vinyl alcohol and ethylene bis stearamide successively by said ratio again, mix.Rotating speed 2000r/min, 10 minutes time, 30 ℃ of temperature.The high material that mixes melt extrudes granulation in reciprocating type single screw extrusion machine, add the polyethylene terephthalate (PET) of linking agent epoxy silane and reactive compatibilizer hydroxyl modification in extrusion by the side loading hole by said ratio.Extrude pellet and carry out last mixing granulator by electromagnetic dynamic plasticizing extruder at last, in extrusion, add nano imvite and biological decomposition promotor phosphorous acid ester/modified starch composition by the side loading hole by said ratio.The working parameter of reciprocating type single screw extrusion machine and electromagnetic dynamic plasticizing extruder is as shown in table 4.
Make full biological degradable composition by above-mentioned steps, can be directly by extruding, injection moulding, being processed into various plastics, as disposable products such as sheet material, film, packing bag, cup, dishes.To make sheet material products is example, and mechanical property and decomposability index are as shown in table 5.
The working parameter of reciprocating type single screw extrusion machine of table 4 and electromagnetic dynamic plasticizing extruder
| The temperature setting (℃) | |||||||||
| Section | One | Two | Three | Four | Five | Six | Seven | Eight | Nine |
| Reciprocating type single screw rod | 150 | 160 | 170 | 160 | 150 | ||||
| Electromagnetic dynamic plasticizing extruder | 140 | 155 | 165 | 180 | 190 | 180 | 170 | 160 | 150 |
The engine speed of single screw extrusion machine: 400r/min, feeding machine: about 4.0r/min, material melts body pressure: about 3.5MPa:
Electromagnetic dynamic plasticizing extruder engine speed: 120r/min, feeding machine: about 18.0r/min, material melts body pressure: about 2.5MPa,
Vibrational frequency: 50Hz, vacuum one: natural exhaust, vacuum two :-0.04MPa.
Table 5 mechanical property and decomposability index
| Project | Achievement data | Reference standard | |
| Mechanical property | Tensile strength | 10-20MPa | ZBG3006-89 |
| Size changing rate | ≤ 60% | ||
| Modulus in tension | 500-800MPa | ||
| Biodegradable (composting mode) | Complete biological decomposition, degradation production is CO 2And H 2O. | ISO14855 ASTMD6400-99 EN13432：2000 | |
Embodiment 4
Each composition weight is formed:
35 parts of modification wheat starches
50 parts of poly butyric esters
1.2 parts on mica (80 nanometer)
7.0 parts of Xylitols
5.0 parts of oxystearic acids
0.8 part of glycidyl methacrylate (GMA)
2.0 parts of methyl tributanoximo silanes
(30/60) 3.0 part of dodecyl acrylate/modified starch composition
Wheat starch is carried out constant pressure and dry to moisture content under 40 ℃ be 8%.The properties-correcting agent Zinic stearas that adds 3.0% (weight) in dried wheat starch is refined to 2800 orders after mixing.Then by said ratio get the modification wheat starch, Xylitol mixes in high-speed mixer, rotating speed 4000r/min, 4 minutes time, add biodegradable polymer poly butyric ester and oxystearic acid successively by said ratio again, mix.Rotating speed 3500r/min, 5 minutes time, 80 ℃ of temperature.The high material that mixes melt extrudes granulation in reciprocating type single screw extrusion machine, add linking agent methyl tributanoximo silane and reactive compatibilizer glycidyl methacrylate (GMA) by said ratio by the side loading hole in extrusion.Extrude pellet and carry out last mixing granulator by electromagnetic dynamic plasticizing extruder at last, in extrusion, add nano mica and biological decomposition promotor dodecyl acrylate // modified starch composition by the side loading hole by said ratio.The working parameter of reciprocating type single screw extrusion machine and electromagnetic dynamic plasticizing extruder is as shown in table 6.
The working parameter of reciprocating type single screw extrusion machine of table 6 and electromagnetic dynamic plasticizing extruder
| The temperature setting (℃) | |||||||||
| Section | One | Two | Three | Four | Five | Six | Seven | Eight | Nine |
| Reciprocating type single screw rod | 105 | 125 | 140 | 130 | 110 | ||||
| Electromagnetic dynamic plasticizing extruder | 180 | 195 | 210 | 220 | 230 | 215 | 205 | 190 | 180 |
The engine speed of single screw extrusion machine: 300r/min, feeding machine: about 8.0r/min, material melts body pressure: about 2.8MPa;
Electromagnetic dynamic plasticizing extruder engine speed: 180r/min.Feeding machine: about 10.0r/min, material melts body pressure: about 3.0MPa,
Vibrational frequency: 20Hz, vacuum one: natural exhaust, vacuum two :-0.02MPa.
Obtain corresponding full biological degradable composition by above-mentioned steps.
Embodiment 5
Each composition weight is formed:
65.0 parts of modification potato starches
26.0 parts on vegetable fibre
6.0 parts of vanadium oxides (20 nanometer)
9.5 parts of stearins
3.0 parts of n-butyl stearate
2.5 parts of ethylene-methyl methacrylate zinc multipolymers
0.2 part of vinyltrimethoxy silane
(20/78) 1.5 part of vinylformic acid octadecanol ester/modified starch composition
With potato starch 100 ℃ and-to be dried to moisture content under the condition of 0.01MPa be 2.O%.In dried potato starch, add the properties-correcting agent stearic acid hydroxyl of 0.5% (weight), be refined to 2500 orders after mixing.Then by said ratio get the modification potato starch, stearin mixes in high-speed mixer, rotating speed 1500r/min, 15 minutes time, add biodegradable polymkeric substance vegetable fibre and n-butyl stearate successively by said ratio again, mix.Rotating speed 2000r/min, 10 minutes time, 25 ℃ of temperature.The high material that mixes melt extrudes granulation in reciprocating type single screw extrusion machine, add linking agent vinyltrimethoxy silane and reactive compatibilizer ethylene-methyl methacrylate zinc multipolymer by said ratio by the side loading hole in extrusion.Extrude pellet and carry out last mixing granulator by electromagnetic dynamic plasticizing extruder at last, in extrusion, add vanadium oxide nanoparticle and biological decomposition promotor vinylformic acid octadecanol ester/modified starch composition by the side loading hole by said ratio.The working parameter of reciprocating type single screw extrusion machine and electromagnetic dynamic plasticizing extruder is as shown in table 7.
The working parameter of reciprocating type single screw extrusion machine of table 7 and electromagnetic dynamic plasticizing extruder
| The temperature setting (℃) | |||||||||
| Section | One | Two | Three | Four | Five | Six | Seven | Eight | Nine |
| Reciprocating type single screw rod | 140 | 150 | 160 | 150 | 140 | ||||
| Electromagnetic dynamic plasticizing extruder | 200 | 215 | 230 | 240 | 250 | 235 | 220 | 205 | 190 |
The engine speed of single screw extrusion machine: 100r/min, feeding machine: about 5.6r/min, material melts body pressure: about 3.0MPa;
Electromagnetic dynamic plasticizing extruder engine speed: 400r/min, feeding machine: about 6.0r/min, material melts body pressure: about 2.5MP,
Vibrational frequency: 30Hz, vacuum one: natural exhaust, vacuum two :-0.06MPa.
Obtain corresponding full biological degradable composition by above-mentioned steps.
Embodiment 6
Each composition weight is formed:
40.0 parts of modified konjaku starch
50.0 parts of polycaprolactone-polylactic-acid block copolymers
3.2 parts of molybdenum oxides (70 nanometer)
4.8 parts of methane amides
2.0 parts of Magnesium Stearates
From 4.5 parts of aggressiveness SurIyn8920
1.0 parts of epoxy silanes
(10/15/70) 2.0 part of linolic acid/vinylformic acid octadecanol ester/modified starch composition
Konjak starch is carried out constant pressure and dry to moisture content under 60 ℃ be 4.5%.In dried konjak starch, add the properties-correcting agent dimethyl dialkyl amine salt of 1.0% (weight), be refined to 2000 orders after mixing.Then by said ratio get modified konjaku starch, methane amide mixes in high-speed mixer, rotating speed 1500r/min, 10 minutes time added biodegradable polymer poly caprolactone-polylactic-acid block copolymer and Magnesium Stearate successively by said ratio again, mixed.Rotating speed 1500r/min, 10 minutes time, 50 ℃ of temperature.The high material that mixes melt extrudes granulation in reciprocating type single screw extrusion machine, add linking agent epoxy silane and reactive compatibilizer from aggressiveness SurIyn8920 by said ratio by the side loading hole in extrusion.Extrude pellet and carry out last mixing granulator by electromagnetic dynamic plasticizing extruder at last, in extrusion, add nano oxidized molybdenum and biological decomposition promotor linolic acid/vinylformic acid octadecanol ester/modified starch composition by the side loading hole by said ratio.The working parameter of reciprocating type single screw extrusion machine and electromagnetic dynamic plasticizing extruder is as shown in table 8.
The working parameter of reciprocating type single screw extrusion machine of table 8 and electromagnetic dynamic plasticizing extruder
| The temperature setting (℃) | |||||||||
| Section | One | Two | Three | Four | Five | Six | Seven | Eight | Nine |
| Reciprocating type single screw rod | 130 | 150 | 160 | 145 | 125 | ||||
| Electromagnetic dynamic plasticizing extruder | 128 | 140 | 150 | 165 | 180 | 170 | 160 | 150 | 120 |
The engine speed of single screw extrusion machine: 220r/min, feeding machine: about 5.0r/min, material melts body pressure: about 2.5MPa;
Electromagnetic dynamic plasticizing extruder engine speed: 260r/min, feeding machine: about 6.5r/min, material melts body pressure: about 3.0MPa,
Vibrational frequency: 40Hz, vacuum one: natural exhaust, vacuum two :-0.04MPa.
Obtain corresponding full biological degradable composition by above-mentioned steps.
Claims (10)
1. full biological degradable composition is characterized in that basic composition is in weight part:
Treated starch 20-80 part of particle diameter≤6.5 micron,
Biodegradable polymkeric substance 10-60 part that plastics-production allows,
Nanometer strengthener 1-6 part,
Softening agent 2-10 part,
Lubricant 1-6 part,
Reactive compatibilizer 0.5-5 part,
Linking agent 0.1-3 part,
Biological decomposition promotor 0.5-3 part,
Wherein: at least aly among the ionic surfactant of treated starch for lipid acid, soap or higher amines salt carry out the natural starch that modification was handled through accounting for starch weight 0.5-5%; Nanometer strengthener is at least a in nano level lime carbonate, clay, mica, vanadium oxide, molybdenum oxide, the polynite; Biological decomposition promotor is by the formed composition of the part by weight of 10-40: 60-90 by unsaturated acid or unsaturated acid ester and starch.
2. full biological degradable composition as claimed in claim 1 is characterized in that said biodegradable polymkeric substance is at least a in polycaprolactone, poly(lactic acid), polyvinyl alcohol, poly butyric ester, poly-hydroxyl valerate, polyglycolic acid, polyesteramide, urethane or their segmented copolymer and the vegetable fibre.
3. full biological degradable composition as claimed in claim 1, it is characterized in that unsaturated acid in the said biological decomposition promotor is at least a in linolic acid, the linolenic acid, unsaturated acid ester is at least a in dodecyl acrylate, vinylformic acid octadecanol ester, the phosphorous acid ester.
4. full biological degradable composition as claimed in claim 1 is characterized in that said softening agent is any one in polyvalent alcohol or methane amide, urea, the stearin
5. full biological degradable composition as claimed in claim 1 is characterized in that said lubricant is at least a in fatty acid amide, fatty acid ester, the soap series lubricant agent.
6. full biological degradable composition as claimed in claim 1, it is characterized in that said reactive compatibilizer is the undecylenic acid in carboxylic acid or the anhydrides compound, maleic anhydride, at least a in the dodecyl cis-butenedioic anhydride, or percentage of grafting is respectively cis-butenedioic anhydride g-polycaprolactone or at least a acid anhydrides in the cis-butenedioic anhydride grafted polyethylene alcohol and the grafts of degradable high polymer of 0.2%-10%, or glycidyl methacrylate, the polyethylene terephthalate of hydroxyl modification, polybutylene terephthalate, polypropylene or polystyrene, or the ethylene-methyl methacrylate zinc multipolymer in the ionic polymer, from aggressiveness Surlyn 8920, at least a among the Surlyn 8660.
7. full biological degradable composition as claimed in claim 1 is characterized in that said linking agent is the silicane linking agent.
8. the method for preparing the described full biological degradable composition of claim 1, after it is characterized in that native starch is dried to moisture content and is 1%-10%, add said properties-correcting agent mixing and be crushed to said particle diameter and do the modification processing, then with the said softening agent that adds successively, biodegradable polymer materials and lubricant thorough mixing, mixture, is extruded and granulation through the Electromagnetic Dynamic mixing extruder is further mixing with the nanometer strengthener of said proportional and biological decomposition promotor behind reciprocating type single screw extrusion machine melting mixing with the linking agent of said proportional and reactive compatibilizer again.
9. preparation method as claimed in claim 8, the extruding pelletization temperature that it is characterized in that said reciprocating type single screw extrusion machine are 100 ℃-180 ℃, and engine speed is 100-400r/min; The extruding pelletization service temperature of electromagnetic dynamic plasticizing extruder is 120 ℃-250 ℃, and engine speed is 100-400r/min, and vibrational frequency is 5-50Hz, and negative pressure of vacuum is 0.02-0.08MPa.
10. the purposes of the described full biological degradable composition of claim 1, it is characterized in that directly making goods, or have biological decomposition performance plastics as mix the addition type masterbatch co-manufactured of using with ordinary resin with full biological decomposition performance according to plastics process for processing mode.
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